Pesticidal acrylonitrile reaction products



United States Patent Office 3,@55,l27 Patented Nov. 20, 1962 3,065,127PESTICAL ACRYLONETRILE REACTEUN PRQDUCTS This invention provides novelcompositions of matter obtained by reaction of acrylonitrile with sulfurmonochloride. The invention also provides biological toxicants in whichsaid compositions are employed as the essential toxicant ingredients.

According to the invention, the presently provided novel reactionproducts are prepared by simply contacting sulfur monochloride with atleast two molar equivalents of acrylonitrile, and allowing the resultingmixture to stand at ordinary or increased temperatures until reaction iscompleted. This can be readily ascertained, e.g., by noting cessation inchange of color and/ or viscosity and/or refractive index of thereaction mixture. The present reaction products are believed to bemixtures of organic, sulfur-containing chloro-nitriles and diversedecomposition products thereof. The reaction mixture components arediificult to separate, but the presently provided complex reactionproducts are of intrinsic utility, e.g., as microbiological toxicants,etc.

It is believed that the reaction of sulfur monochloride with two molarequivalents of acrylonitrile probably proceeds with the primaryformation of isometric chloro cyano disulfides, thus:

(III) cicnzc in-crv S OICHzICHON l CICH CHGN CICH2CHCN Either the chlorocyano disulfides or the chloro cyano monosulfides may undergo somedehydrochlorination.

The identity of any one of the possible isomeric chloro cyano disulfides or sulfides or their dehydrohalogenation products has provedimpossible to establish; hence, we do not wish to be bound by the abovespeculative structures.

That the present products result from the reaction of one mole of thesulfur monochloride with two moles of acrylonitrile is evident fromconsumption of these reactants in the 1:2 ratio. Thus, the reactionproduct obtained by heating, at, say, 50 C. to 60 C. a mixture of onemole of sulfur monochloride and two moles of acrylonitrile has a bOilingpoint and refractive index above that of either said monochloride orsaid nitrile, and analyses by both physical and chemical methods showthe presence in said reaction product of the elements chlorine andsulfur and of the cyano (-CN) radical. We have found, on the other hand,that when one mole of sulfur monochloride is treated under the sameconditions with only one molerather than two moles-of acrylonitrile,most of said monochloride is recovered unchanged, and the very smallamount of higher boiling product which is obtained decomposes uponstanding for a short time under atmospheric conditions.

Since formation of the present complex mixture of sulfur-containingnitriles consumes approximately two moles of acrylonitrile per mole ofthe sulfur monochloride, these reactants are advantageously present instoichiometric proportions. However, an excess of the acrylonitrile maybe used if desired to serve, e.g., as a reaction diluent. Extraneousinert solvents or diluents may like wise be employed. Such suitablematerials include, e.g., carbon tetrachloride, chloroform, ethylenedichloride, dioxane, ether, etc. While the reaction will take placeWithout application of external heat, it is accelerated by moderateheating. Temperatures of, say, 25 C. to 180 C., and preferably of from40 C. to C., are employed. The use of catalysts is generally notnecesesary, although acid catalysts and acidic reaction media may beemployed. Since acrylonitrile is readily polymerizable, an inhibitor ofpolymerization may be included in the reaction mixture, particularlywhen operating at the higher temperatures. The reaction may also befacilitated by conducting it under superatmospheric pressure.

The time required to complete the reaction will depend, of course, onother operational conditions, e.g., temperature, pressure, presence orabsence of diluent and/or catalyst, reactant quantities, details ofapparatus, etc. The reaction may be conducted batch-wise or bycontinuous procedures.

Conveniently, the course of the reaction may be followed by observingthe change in color of the reaction mixture. As the reaction proceeds,the color of the reaction mixture gradually darkens, usually changingfrom a clear yellow to a deep or brownish red by the time all of thesulfur monochloride is reacted. On completion of the reaction, the 2:1acrylonitrile-sulfur monochloride re action product may be isolated byconventional methods, e.g., by evaporation of any solvents, by washingand/or decantation to remove unreacted acrylonitrile, etc.

To the best of our knowledge, the presently provided reaction productsof sulfur monochloride with acryloni trile are complex mixtures ofisomeric saturated and unsaturated sulfur-and chlorine-containing cyanocompounds. The constituents are difiicultly separable, and thecomposition of the present mixture of reaction products has not beenprecisely established. The presently obtained reaction products havebacteriostat and fungistat properties and are useful as the activeconstituents of microbiological toxicant compositions. As will be shownhereinafter, at concentrations of as low as, say, 10 ppm. they entirelyprevent growth of a variety of bacteria and fungi. The reaction productof this invention can be used as a preservative, e.g., in leather, paperand fabrics, or in paints and varnishes to render them proof againstmildew or fungus attack.

The present reaction products may further be used as nematocides,insecticides, herbicides, etc. They are also of utility as chemicalintermediates whereby the cyano radical thereof is converted to thecarboxylic --COOH radical. the chlorine radical replaced by otherradicals, e.g., alkoxy, amino, phosphinyl, or phosphate radicals, andthe sulfide or disulfide radicals converted by oxidation into sulfoxidesor sulfones.

The present invention is further illustrated, but not lim ited, by thefollowing examples:

Example 1 Into a 500 ml. flask, there was placed 138 g. (1.0 mole) ofsulfur monochloride (S Cl 150 ml. of carbon tetrachloride and 106 g.(2.0 moles) of acrylonitrile. The whole was heated with stirring, at atemperature of 60 C. for three hours, allowed to stand overnight at roomtemperature, and then heated again at 5560 C. for one hour. Distillationof the resulting reaction mixture under partial vacuum to remove solventand material boiling up to 34 C./0.2 mm., gave as residue 126 g. of avery viscous liquid which was converted to a red, resinous product uponcooling.

A portion of the resinous product was extracted with a benezene hexanemixture and the resulting solution evaporated to dryness to give abenzene extract (A) and a benzene-insoluble portion (8). infra-redanalysis of (A) and (B) after evaporation of all solvents showed CENabsorption at 2360 cm. for both (A) and (B). Also, for both (A) and (B)the -CCl linkage was indicated at about 720 cmf Elemental analysesshowed the presence of chlorine and sulfur in both (A) and (B).

Example 2 To a mixture consisting of 138 g. (1.0 mole) of sulfurmonochloride and 150 ml. of carbon tetrachloride, there was graduallyadded 106 g. (2.0 moles) of acrylonitrile. The whole was brought to atemperature of 55 C. and maintained at this temperature for 10 minutes.It was then allowed to stand overnight at room temperature and thenheated again to 60-70 C. until evolution of some hydrogen chloride wasnoted. The reaction mixture was then cooled and the carbon tetrachloridestripped therefrom in vacuo to 50 C./13 mm. The residue was taken upwith benzene and acetone and all solvents and unreacted sulfurmonochloride were stripped ofi by distilling up to a pot temperature of70 C./0.51.0 mm. There was thus obtained as residue 143 g. of the red,glassy 2:1 acrylonitrile-sulfur monochloride reaction product, solublein benzene and insoluble in acetone and analyzing as follows:

Percent C 20.49 Percent H 1.51 Percent Cl 26.12 Percent N 7.24 Percent S4563 Example 3 This example describes microbiological evaluation of the2:1 acrylonitrile-sulfur monochloride reaction prodnot of Example 2.

A 1.0% solution of said reaction product was prepared in acetone andadded to sterile melted nutrient agar to give an 0.1% (1 part ofreaction product per 1,000 parts of agar) concentration of the testcompound. This was further diluted with additional melted agar to give1:10,000 and 1:100,000 dilutions of said reaction product in the agar.The various solutions were then respectively poured into Petri dishesand allowed to harden. Plates thus prepared were inoculated with thetest organisms shown below and the inoculated plants were incubated for48 hours at a temperature of 25 C. Inspection of the inoculated platesat the end of that time showed the lowest concentration at which nogrowth occurred to be 1: 10,000 for the following organisms:

Streptococcus faecalz's ATCC 9790 No growth Bacillus cereus var.mycoides IPC 509 N growth Cornyebactcriam diphtcriae ATCC 296 No growthBacterium ammoniagenes ATCC 6871 No growth Erwinia atroseptica ATCC 7404No growth Salmonella typhosa-Hopkins Strain No growth Aspergillus nigerIPC 144 No growth Memnoniella echinata ATCC 9597 No growth Trichodermasp. T-l ATCC 9645 No growth Chaetomium globosum USDA l032.4 No growthAspergillus oryzae ATCC 10196 No growth The lowest concentration atwhich no growth occurred was 1:l00,000 for the following organisms:

Micr c0ccus pyogenes var. aareus ATCC 6538 No growth MycobacteriumplzlciSt. Louis No growth Proteus vulgaris-Lambert No growth Penicilliamexpansam IPC 126 N0 growth Trichophyt n mentagrophytes ATCC 9129-- Nogrowth Fomes annosus FPL 517 No growth Hormisciam gelatinosum FPL 595 Nogrowth Ceratostomclla pilz'fera ATCC 8713 No growth Claa'osporiumlzerbaram ATCC 6506 No growth Alternaria tenuis ATCC 11612 N0 growthMyrothecium verracaria ATCC'9095 No growth Bacillus subtilis-Lambert Nogrowth Stemphylium sarcinaeforme-U. of lll No growth Monoliniafracticola-U. of I11 No growth Pscudomonas phaseolic0laUSDA No growth Itwill be readily seen from the above that the presentacrylonitrile-sulfur monochloride reaction product is effective insuppressing the growth of both gram negative and gram positive bacteriaas well as that of various fungi and molds. At concentrations which aresomewhat higher than those required for the prevention ofmicrobiological growth, the present 2:1 acrylonitrile-sulfurmonochloride reaction products possess herbicidal and insecticidalactivity.

When used either as microbiological toxicants or as insecticides orherbicides, the present reaction products are advantageously employed inthe form of suspensions or emulsions. Since the reaction products areeffective bacteriostats and fungistats when employed in very smallconcentrations, commercial toxicants comprising the reaction productsmay contain only minor proportions thereof. Oil-in-water emulsionscontaining, say, from 0.001% to 0.1% by weight of the present reactionproducts based on the total weight of the emulsion are useful. The wordoil is here used to designate any organic liquid which is insoluble inwater. Emulsifying agents which may be employed are those used in theart for the preparation of oil-in-water emulsions, e.g., long-chainedalkylbenzenesulfonates, polyalkylene glycols, long-chain alkylsulfosuccinates, etc. For these and related biological toxicantpurposes, the reaction products may be incorporated into inert carriersgenerally. Thus they may be mixed with solid carriers such as clay,talc, pumice and bentonite to give toxicants dusts. We have found,however, that the emulsions possess an improved tendency to adhere tothe treated surfaces so that less of the active ingredient, i.e., theacrylonitrile-sulfur monochloride reaction product, is required whenapplied in the emulsion form.

This application is a division of our copending application, Serial No.690,423, filed October 16, 1957, now US. Patent No. 2,993,037.

What we claim is:

l. A composition effective against bacteria and fungi comprising anoil-in-water emulsion of a complex mixture of compounds containingcarbon, hydrogen, sulfur, chlorine and cyano radicals, said mixturehaving been obtained by the reaction of one mole of sulfur monochloridewith two moles of acrylonitrile at a temperature of 25 C. to C.

2. A composition effective against bacteria comprising an oil-in-wateremulsion of a bacteriostatic quantity of a complex mixture of compoundscontaining carbon, hydrogen, sulfur, chlorine and cyano radicals, saidmixture having been obtained by the reaction of one mole of sulfurmonochloride with two moles of acrylonitrile at a temperature of 25 C.to 100 C.

3. A composition effective against fungi comprising an oil-in-wateremulsion of a fungistatic quantity of a complex mixture of compoundscontaining carbon, hydrogen, sulfur, chlorine and cyano radicals, saidmixture having been obtained by the reaction of one mole of sulfurmonochloride with two moles of acrylonitrile at a temperature of 25 C.to 100 C.

4. The method of inhibiting the growth of fungi and bacteria whichcomprises exposing them to a growth-inhibiting quantity of a compositioncomprising as the essential effective ingredient a complex mixture ofcompounds containing carbon, hydrogen, sulfur, chlorine and cyanoradicals, said mixture having been obtained by the reaction of one moleof sulfur monochloride with two moles of acrylonitrile at a temperatureof 25 C. to 100 C.

5. The method of inhibiting the growth of fungi which comprises exposingthem to a growth-inhibiting quan- 'ty of a composition comprising as theessential effective ingredient a complex mixture of compounds containingcarbon, hydrogen, sulfur, chlorine and cyano radicals, said mixturehaving been obtained by the reaction of one mole of sulfur monochloridewith two moles of acrylonitrile at a temperature of 25 C. to 160 C.

6. The method of inhibiting the growth of bacteria which comprisesexposing them to a growth-inhibiting quantity of a compositioncomprising as the essential effective ingredient a complex mixture ofcompounds containing carbon, hydrogen, sulfur, chlorine and cyanoradicals, said mixture having been obtained by the reaction of one moleof sulfur monochloride with two moles of acrylonitrile at a temperatureof 25 C. to 100 C.

No references cited.

4. THE METHOD OF INHIBITING THE GROWTH OF FUNGI AND BACTERIA WHICHCOMPRISES EXPOSING THEM TO A GROWTH-INHIBITING QUANTITY OF A COMPOSITIONCOMPRISING AS THE ESSENTIAL EFFECTIVE INGREDIENT A COMPLEX MIXTURE OFCOMPOUNDS CONTAINING CARBON, HYDROGEN, SULFUR, CHLORINE AND CYANORADICALS, SAID MIXTURE HAVING BEEN OBTAINED BY THE REACTION OF ONE MOLEOF SULFUR MONOCHLORIDE WITH TWO MOLES OF ACRYLONITRILE AT A TEMPERATUREOF 25*C. TO 100*C.